Silicone product, a lighting unit comprising the silicone product and method of manufacturing a silicone product

ABSTRACT

A silicone product, a lighting unit comprising the silicone product, and a method of manufacturing a silicone product are provided. The silicone product comprises polymeric material, luminescent material and filler particles. The polymeric material comprises a material of the group of polysiloxanes. The polymeric material being light transmitting. The luminescent material comprises particles which have at least in one dimension a size in the nanometer range. The luminescent material is configured to absorb light of a first spectral range and to convert a portion of the absorbed light into light of a second spectral range. The filler particles are of a light transmitting inert material. The filler particles are miscible with the luminescent material. The filler particles are provided in the polymeric material. The particles of luminescent material are distributed along a surface of the filler particles.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 14/413,240 filed on Jan. 7, 2015, titled “SILICONE PRODUCT, ALIGHTING UNIT COMPRISING THE SILICONE PRODUCT AND METHOD OFMANUFACTURING A SILICONE PRODUCT”, which is a §371 application ofInternational Application No. PCT/IB2013/055655 filed on Jul. 10, 2013,which claims priority to U.S. Provisional Patent Application No.61/670,178 filed on Jul. 11, 2012. U.S. patent application Ser. No.14/413,240, International Application No. PCT/IB2013/055655, and U.S.Provisional Patent Application No. 61/670,178 are incorporated herein.

FIELD OF THE INVENTION

The invention relates to silicone products which comprise a luminescentmaterial. The invention further relates to a lighting unit comprisingthe silicone product and a method of manufacturing a silicone productcomprising immobilized luminescent materials

BACKGROUND OF THE INVENTION

In many lighting applications, especially in lighting application inwhich Light Emitting Diodes (LEDs) are used, silicone is used foroptical elements, such as for example, a lens or a light guide forguiding the light to a light exit window or improve the outcoupling oflight from the LED. Silicones are sufficiently stable in LED applicationand are able to withstand the relatively high light dosages and hightemperatures of LED applications. Such optical elements can easily bemanufactured from a silicone resin.

Luminescent quantum dots are a promising material for creating lightingassemblies which emit a specific color of light, such as, for example, alighting assembly which emits white light. The luminescent quantum dotsabsorb a portion of light emitted by, for example, a LED and convert thelight towards light of another color. Quantum dots provide a highefficiency and relatively long lifetime if the quantum dots are wellspatially separated in the matrix material. Because of the advantageouscharacteristics of silicone, the quantum dots are preferably embedded insilicone.

However, quantum dots and similar luminescent materials (such as quantumrods or quantum tetrapods) cannot be easily dispersed in silicone. It isknown that quantum dots can easily be dispersed in liquids like tolueneand some acrylic mixtures without forming clusters of quantum dots—insuch liquids the quantum dots will be well spatially separated. Quantumdots are very small particles and during manufacturing they need to beadded as a mixture of a solvent and quantum dots to a silicone resin.Quantum dots are not compatible with silicone resins and flocculation ofthe quantum dots occurs when they are mixed with a silicone resin. Otherterms used for flocculation are aggregation, agglomeration andclustering. If quantum dots form agglomerates in which their mutualseparation is less than a few nanometers (e.g. smaller than 7nanometers), the quantum efficiency of the quantum dots reduces and afaster degradation upon irradiation is observed. Further, the quantumdots can still, to a limited extent, be mobile within the silicone resinand flocculation may slowly continue resulting in an even lower quantumefficiency. It is believed that the reduction of the quantum efficiencyis the result of the occurrence of concentration quenching due toexcitation and/or charge transfer between quantum dots. Further,undesired chemical reactions between neighboring quantum dots may alsocause a degradation of the aggregates of quantum dots.

Published patent application US2012/0045850 discloses a materialcomprising quantum dots that is better compatible with many materials,such as water. The solution of the patent application may result in amaterial which is more compatible with silicone. The solution of thecited patent application is to create silica particles embedding thequantum dots. As silica particles are part of many silicone formulationsthe resulting silica coated quantum dots can easily be mixed intosilicone resins.

In the approach in US2012/0045850 water is present in the reactionmixture preparing the silica nanoparticles. As for many quantum dots thepresence of water either reduces the quantum efficiency directly and/oraccelerates the degradation, the light conversion can be low ordecreasing too rapidly over time. It seems that the use of, for example,water in the steps of creating the silica nanoparticles results in thecreation non-light-emitting quantum dots. Thus, the quantum dotsembedded in the silica nanoparticles of the cited patent show arelatively small light conversion efficiency and when the silicananoparticles of the cited patent application are used in the silicone,the light conversion efficiency can be expected to be relatively low.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a silicone product whichcomprises nanometer sized luminescent particles which have, in use, arelatively large quantum efficiency.

A first aspect of the invention provides a silicone product. A secondaspect of the invention provides a lighting unit. A third aspect of theinvention provides a method of manufacturing a silicone productcomprising immobilized luminescent material. Advantageous embodimentsare defined in the dependent claims.

A silicone product in accordance with the first aspect of the inventioncomprises polymeric material, luminescent material and filler particles.The polymeric material comprises a material of the group ofpolysiloxanes, the polymeric material being light transmitting. Theluminescent material comprises particles which have at least in onedimension a size in the nanometer range. The luminescent material isconfigured to absorb light of a first spectral range and to convert aportion of the absorbed light into light of a second spectral range. Thefiller particles are of a light transmitting inert material. The fillerparticles are miscible with the luminescent material. The fillerparticles are provided in the polymeric material. The particles ofluminescent material are distributed along a surface of the fillerparticles.

Another term often used for the polymeric material comprising a materialof the group of polysiloxanes is silicone. Polysiloxanes are polymericmaterials with the general formula [R2SiO]m wherein R is an organicgroup, such as, for example, methyl, ethyl or phenyl. The backbone ofthe molecules is an inorganic Silicon-Oxygen chain . . .—Si—O—Si—O—Si—O— . . .

The filler particles and the particles of the luminescent material aremiscible, which means that the particles of the luminescent material andthe filler particles both remain distributed in a solvent without beingsubject to extensive agglomeration, aggregation and/or flocculation. Inpractical embodiments it means that the filler particles and theparticles of luminescent material can both be homogeneously mixed intoat least one type of solvent.

In a subsequent step, the colloidal stability of the luminescentparticles is reduced causing them to flocculate. Due to the presence ofthe filler particles with excess surface area, the luminescent particleswill flocculate onto the surface of the filler particles. Such a processin which one type of particles flocculates onto another type ofparticles is called heteroflocculation. Luminescent material and thefiller particles do not have the tendency to stay away from each otherin the solvent. When the luminescent material and the filler particleswould be non-miscible, a non-homogeneous mix would be obtained in thesolvent and, optionally, the luminescent material and/or the fillerparticles would flocculate.

The International Union of Pure and Applied Chemistry (IUPAC)distinguish different types of stability for colloidal system (a mixtureof particles which are dispersed in a liquid medium). In this currentinvention it is assumed that the silicone product is colloidally stable.The definition of “colloidally stable” relates to the possibility toobtain a homogeneous solution in which as well as the luminescentmaterial and the filler particles are solved and/or dispersedhomogeneously. The filler particles and the luminescent material areboth colloidally stable in a group of liquids. According to the IUPAC,colloidally stable means “the particles do not aggregate at asignificant rate. An aggregate is, in general, a group of particles(which may be atoms or molecules) held together in any way. Aggregationis the process or the result of the formation of aggregates. When acolloidally system is colloidally unstable (i.e. the rate of aggregationis not negligible) the formation of aggregates is called coagulation orflocculation. These terms are often used interchangeably, but someauthors prefer to introduce a distinction between coagulation, implyingthe formation of compact aggregates, leading to the macroscopicseparation of a coagulum; and flocculation, implying the formation of aloose or open network which may or may not separate macroscopically. Inmany contexts the loose structure formed in this way is called a floc.The rate of aggregation is in general determined by the frequency ofcollisions and the probability of cohesion during collision. If thecollisions are caused by Brownian motion, the process is calledperikinetic aggregation; if by hydrodynamic motions (e.g. convection orsedimentation) one may speak of orthokinetic aggregation. In the contextof this invention the distinction between “coagulation” or“flocculation” is not relevant. As soon as the luminescent materialaggregates, the quantum efficiency decreases and this is prevented bythe invention.

As a consequence of the invention, inside the polymeric materialcomprising the polysiloxane the luminescent particles are distributedalong the surface of the filler particles. Thus, the tendency of theparticles of the luminescent material to agglomerate, aggregate and/orflocculate inside the polymeric material comprising a polysiloxane isreduced, or even fully stopped, because the particles of the luminescentmaterial are located at the surface of filler particles. In other words:within the polymeric material the luminescent particles are immobilized,because they are in contact with a filler particles, and they do notmove anymore towards each other in the (cured) polymeric material, and,thus, they do not aggregate anymore. There is no tendency to formhomoaggregates. Thus, most of the particles of the luminescent materialdo not touch other particles of the luminescent material, which meansthat they are well spatially separated from each other. As discussedbefore, a good spatial separation of the particles of luminescentmaterial results in a relatively high quantum efficiency. Consequently,the silicone product exhibits, when being irradiated with light that isbeing absorbed and converted by the luminescent material, a relativelylarge color conversion efficiency.

The particles of the luminescent material have in at least one dimensiona size in the nanometer range. This means, for example, that, if theparticles are substantially spherical, their diameter is in thenanometer range. Or, this means, for example, if they are rod-shaped,that a size of a cross-section of the wire is in one direction in thenanometer range. A size in the nanometer range means that the size inthe at least one dimension is at least smaller than 100 nanometers,thus, smaller than 0.1 micrometer, and larger or equal to 0.5 nanometer.In an embodiment, the size in one dimension is smaller than 50nanometer. In another embodiment the size in one dimension is in therange from 2 to 20 nanometer. Most luminescent material with a size inthe nanometer range in at least one dimension show quantum confinement,which means that the color of the light emitted by the material (as aconsequence of absorbing light) strongly depend on their size. Thisapplies to most quantum dots, however, specific quantum dots do not showquantum confinement. Also the quantum dots which do not show quantumconfinement are subject to the same effects as the quantum dotsdiscussed in the background of the art section (flocculation insilicone).

In an embodiment, it might be that the filler particles are not fullymiscible with the (silicone) polymeric material such that the fillerparticles agglomerate, aggregate and/or flocculate up to some degree.However, the flocculation of the filler particles does not necessarynegatively influence the efficiency of the particles of luminescentmaterial. The particles of the luminescent material are distributedalong the surface of the filler particles and, as such, when the fillerparticles touch each other, the particles of the luminescent materialare still spatially separated from other particles of luminescentmaterial by the filler particles.

Distributed along the surface of the filler particles means that theparticles of the luminescent material are in contact with the surface ofthe filler particles and that at different portions of the surfaceluminescent particles may be found. Being in contact with each otherdoes not directly imply that the luminescent particles and fillerparticles are fused or have a sort of binding as the result of achemical reaction. The particles are still individual particles and canbe identified separately. The particles are adjacent in the meaning of‘they have common border or endpoint’, or they adjoin in the meaning of‘to lie next to each other or being in contact’, and, thus, theparticles are neighboring.

Further, in the context of this document, light transmitting means thatlight is transmitted through the material—in other words, if a lightbeam impinges on a surface of the material, at least some light isemitted at the same or other surfaces of the material. Thus, not alllight is absorbed, for example, not more than 15% of the light isabsorbed. In another embodiment, light transmitting means that not morethan 10% of the light is absorbed. In yet a further embodiment, lighttransmitting means that not more than 10% of the light is absorbed. Itis to be noted that transparent and translucent are terms falling withinthe scope of light transmitting. In the context of the invention, thefiller particles are of a light transmitting material, but it is to benoted that the silicone product as a whole may absorb light, forexample, the luminescent particles absorb light of a specific color andconvert a portion of the absorbed light to light of another color.

Inert materials are materials which do not react with at least thematerials which are used in the context of this invention under thecircumstances described in the context of this document. Thus, the inertmaterials are not chemically reactive. This does not exclude that, underspecific circumstances, the inert materials may be involved in achemical reaction, but then large amounts of energy from heat, pressureor radiation are needed and often catalysts are used to assist thereactions.

Optionally, the filler particles are larger than the particles ofluminescent material. If the filler particles are larger they have arelatively large surface compared to the size of the particles ofluminescent material and, thus, when the particles of luminescentmaterial are distributed along the surface of the filler particles, theyare spatially well separated. Thus, the chance that particles ofluminescent material are too close to each other such that their quantumefficiency drops is smaller. Further, within the polymeric materialparticles may move (as long as the polymeric material is not cured to asolid state), and larger particles move much slower than smallerparticles. Thus, the smaller luminescent particles which are in contactwith the larger filler particles move much slower through the polymericmaterial, and, thus they are better immobilized and do not aggregate. Itis to be noted that the size of the filler particles may not become toolarge. Very large filler particles have a relatively small amount ofsurface area per gram of the material, and, thus, less space betweenparticles of the luminescent material may be present between particlesof the luminescent material which are in contact with the surface of asingle filler particle. In an embodiment, the size of the fillerparticles is below 5 micrometer, or, in another embodiment, below 1micrometer, or, in a further embodiment, below 500 nanometers. In yetanother optional embodiment below 250 nanometers, and in a furtheroptional embodiment smaller than 100 nanometers.

Optionally, the filler particles are not smaller than the particles ofluminescent material.

Optionally, the luminescent material comprises at least one of quantumdots, quantum rods and quantum tetrapods. Thus, the particles which showquantum confinement and have at least in one dimension a size in thenanometer range are quantum dots, quantum rods or quantum tetrapods. Thematerials of this optional embodiment are incompatible with siliconeresins, thus, with polymeric material comprising polysiloxane.

Optionally, at least 60% of the particles of the luminescent materialare separated far enough from other particles of the luminescentmaterial to prevent a reduction of quantum efficiency of theseparticles. In an embodiment at least 75% of the particles of theluminescent material are separated far enough from each other. Inanother embodiment, at least 90% of the particles of the luminescentmaterial are separated far enough from each other. Separated far enoughfrom each other means that these particles at least do not touch eachother, and may mean in an optional embodiment that concentrationquenching does not occur. Further, it was observed that when theluminescent particles are located very close to each other, for example,at 7 nanometers distance, the quantum efficiency drops. The effect ofthis optional embodiment is that the quantum efficiency, and thus thecolor conversion efficiency, of the silicone product as a whole isrelatively high. In an embodiment, the particles of the luminescentmaterial that are separated far enough from each other have at least adistance of 10 nanometers between the particles without anotherparticles of the luminescent material in between them.

Optionally, the filler particles are silica particles or the fillerparticles comprise a material of one of the groups of alumina, titania,silica materials or a clay. Silica particles are often used in polymericmaterials which comprise polysiloxane and can easily be mixed with suchpolymeric materials. In general, silica particles have a refractiveindex which is close to the refractive index of polymeric materialswhich comprise polysiloxane and, thus, light is not much refracted atthe interfaces between the silica particles and the polysiloxanematerial and not much light is reflected a these interfaces. Thus, thesilicone product remains relatively transparent and does not muchscatter light. In other embodiments, scattering of light is required,and materials used for the filler particles have a refractive index thatdiffers more from the refractive index of the polymeric materialcomprising polysiloxane. Transparent particles of clay have often arelatively flat shape which results in a relatively large outer surfacealong which the particles of luminescent materials can be distributed,and, thus, a good spatial separation of the particles of luminescentmaterials is obtained.

Optionally, the particles of the luminescent material comprise a firstlayer of organic material at their surface. Optionally, the fillerparticles comprise a second layer of organic material at their surface.The first layer and/or the second layer are applied to, respectively,the particles of luminescent material and/or the filler particles tomake them miscible in the solvents used in preparation processes.Optionally, at least one of the first layer and the second layer oforganic material is a monolayer of the organic material. A monolayer isthe amount of organic material needed to form a densely packed, onemolecule thick layer. Especially when the first layer and/or the secondlayer are similar organic layers, the filler particles and the particlesof luminescent material are better miscible with each other in a solventand, thus, the particles of luminescent material can be processed to bebetter spatially separated along the surface of the filler particles—inother words, the particles of luminescent material do not tend toflocculate or agglomerate.

Optionally, not more than 20% of the surface of the filler particles iscovered by particles of the luminescent material. When less than 20% ofthe surface of the filler particles is covered by the particles ofluminescent material, the particles of luminescent material are probablywell spatially separated. It may be tested whether the silicone productfulfills the condition of this optional embodiment by makingTransmission Electron Microscopy (TEM) images of the silicone product,determining the size of the filler particles and calculating itscorresponding surface area, determining the number of particles ofluminescent material at the surface of the filler particles, determiningthe size of the particles of luminescent material, calculating thesurface of the filler particles covered by the luminescent particles,and calculating the relative amount of the surface of the fillerparticles covered by the luminescent particles. It is to be noted thatthe relative amount of the surface of the filler particles covered bythe particles of luminescent material is an average number and that thesurface of individual filler particles may be covered by a higherpercentage. In another optional embodiment not more than 10% of thesurface of the filler particles is covered by particles of theluminescent material. In a further optional embodiment not more than 5%of the surface of the filler particles is covered by particles of theluminescent material.

Optionally, the relative amount of luminescent material is at least 0.05weight percent of the silicone product and the relative amount of theluminescent material is not more than 10 weight percent of the siliconeproduct. Such a relative amount of particles of the luminescent materialis in general enough to provide the required light conversion by theseluminescent particles (which, of course, also depends on theconfiguration of the light emitting device). Further, in the invention,if the relative amount is below 10 wt %, the particles of luminescentmaterial can be advantageously distributed along the surface of thefiller particles without being in contact with other particles of theluminescent material.

Optionally, the relative amount of the filler particles is not more than40 weight percent of the silicone product, and the relative amount ofthe filler particles is at least twice the relative amount ofluminescent material expressed as a weight percentage of the siliconeproduct. In practical embodiments, the amount of filler particles shouldbe below 40 wt % in order to maintain advantageous properties of thepolymeric material which comprises a polysiloxane.

Optionally, the largest size of the filler particles is smaller than 5micrometer. In another optional embodiment, the largest size of thefiller particles is smaller than 1 micrometer. In a further optionalembodiment, the largest size of the filler particles is smaller than 500nanometers. Largest size means in the context of this document: across-sectional size of the filler particle in a specific direction andin all other directions the cross-sectional size is smaller than thelargest size. Thus, if the filler particles are substantially spherical,the diameter of the particles is less than 500 nanometers. If the fillerparticles have a rod-shape, the length of the rod is less than 500nanometers. If the filler particles are flat shapes, any line that canbe drawn in the flat plane is shorter than 500 nanometers.

Optionally, the polymeric material has a first refractive index and thefiller particles have a second refractive index. The largest size of thefiller particles is smaller than 100 nanometers if the absolutedifference between the first refractive index and the second refractiveindex is larger than 0.3. The larger the difference in refractiveindices between the two types of material the more reflection andrefraction occurs at the interfaces between the two materials, whichresults in a diffusion of the light which transmits through the siliconeproduct. In specific embodiments this is undesired and it is requiredthat the silicone product is substantially transparent. This can beobtained by using materials of about the same refractive index, whichmeans that the difference in refractive indices is less than 0.1, orwhich can be obtained by reducing the size of the filler particles independence of the difference in refractive indices. The numbers providedin this optional embodiment result in a silicone product whichdiffuses/scatters light only up to a limited extent. It is further to benoticed that transparency does not necessary only dependent on thedifferences in refractive indices. It also depends on the particles sizeand the particle volume fraction. If the silicone product is, forexample, applied in a thin layer of, for example, 1 micrometer, a layercan still be transparent when 20 nanometer TiO2 are present in thelayer. Further, the relative amount of filler particles also contributesto the amount of transparency.

Optionally, the silicone product is a resin and the silicone is asilicone resin. When the silicone product is a resin it is, up to someextent, flexible/liquid and can be formed into different shapes. Withspecific treatments the resin may be cured such that a solid siliconeproduct is obtained.

According to a second aspect of the invention, a lighting unit isprovided which comprises a light source and a silicone product accordingto the first aspect of the invention. The silicone product is arrangedto receive light from the light source.

The lighting unit according to the second aspect of the inventionprovides the same benefits as the silicone product according to thefirst aspect of the invention and has similar embodiments with similareffects as the corresponding embodiments of the silicone product.

According to a third aspect of the invention, a method of manufacturinga silicone product comprising immobilized luminescent material isprovided. The method comprises the steps of: i) obtaining a mixture offiller particles of a light transmitting inert material and luminescentmaterial comprising particles showing quantum confinement and having atleast in one dimension a size in the nanometer range, wherein theparticles of the luminescent material are situated at a surface of thefiller particles; ii) mixing the mixture with a polymeric materialcomprising a material of the group of polysiloxanes.

The method according to the third aspect of the invention provides thesame benefits as the silicone product according to the first aspect ofthe invention and has similar embodiments with similar effects as thecorresponding embodiments of the silicone product.

Optionally, the step of obtaining a mixture comprises the sub steps of:a) obtaining a first homogeneous mixture of the filler particles in afirst solvent, b) obtaining a second homogeneous mixture of theluminescent material in a second solvent, c) mixing the first homogenousmixture with the second homogeneous mixture to obtain a thirdhomogeneous mixture, and d) flocculating the luminescent material on thefiller particles by changing the solvent composition of the thirdhomogeneous mixture or by changing the solvent quality of the thirdhomogeneous mixture.

The method to obtain the mixture starts with obtaining the firsthomogeneous mixture and the second homogeneous mixture. These mixturesmay be obtained directly from a manufacturer of such homogeneousmixtures, or may be prepared by, for example, diluting a stock solutionin the same solvent as the solvent of the stock solution. Subsequentlythese homogeneous mixtures are mixed to obtain a third homogeneousmixture. The third homogeneous mixtures can only be obtained if thefirst solvent and the second solvent do not cause an aggregation orflocculation of the luminescent material and the filler particles.Subsequently, in the step of flocculating the luminescent material onthe filler particles, a third solvent or additive is added to the thirdhomogeneous mixture which causes a change of the solvent composition ofthe third homogeneous mixture such that the luminescent materialflocculates to the surface of the filler particles and the combinationof the filler particles with luminescent material flocculates.Alternatively, the quality of the solvent composition of the thirdhomogeneous mixture is changed by, for example, changing the temperatureof the solvent composition, such that the luminescent materialflocculates on the filler particles. Often the term heteroflocculationis used for this process. Subsequently, in an optional embodiment, thesolvents (the first solvent and/or the second solvent) are removed. Thismay be done, for example, by evaporating the solvents. Alternatively thesolvents are removed after mixing the obtained mixture of fillerparticles and the luminescent material with the polymeric material.

The method of obtaining the mixture of the filler particles and theluminescent material is an effective and an efficient way of obtainingthe silicone product of the invention. It was seen that the particles ofthe luminescent material are well distributed along the surface of thefiller particles and that most of the particles of the luminescentmaterial are not located too close to each other.

It is to be noted that the first solvent and the second solvent may bethe same solvent.

These and other aspects of the invention are apparent from and will beelucidated with reference to the embodiments described hereinafter.

It will be appreciated by those skilled in the art that two or more ofthe above-mentioned options, implementations, and/or aspects of theinvention may be combined in any way deemed useful.

Modifications and variations of the product and/or the method, whichcorrespond to the described modifications and variations of the product,can be carried out by a person skilled in the art on the basis of thepresent description.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 schematically shows an embodiment of the silicone product,

FIG. 2 schematically shows an embodiment of a filler particle with twoparticles of a luminescent material being in contact with a surface ofthe filler particle,

FIG. 3 schematically shows a lighting unit according to the secondaspect of the invention, and

FIG. 4 schematically presents an embodiment of a method of manufacturinga silicone product.

It should be noted that items denoted by the same reference numerals indifferent Figures have the same structural features and the samefunctions. Where the function and/or structure of such an item have beenexplained, there is no necessity for repeated explanation thereof in thedetailed description.

The Figures are purely diagrammatic and not drawn to scale. Particularlyfor clarity, some dimensions are exaggerated strongly.

DETAILED DESCRIPTION

A first embodiment is shown in FIG. 1. FIG. 1 schematically shows, in across-sectional view, an embodiment of the silicone product 100. Theschematic presentation of FIG. 1 is an enlargement and with a dashedline a virtual border of the product 100 is drawn—however, in practicalembodiments, the shown enlargement is only a fraction of a much largerquantity of the silicone product 100. Further, the presented siliconeproduct 100 may be a solid material, or may be a resin which comprisesother molecules (not shown) for creating the semi-fluid state of thematerial (such materials are, for example, monomers, macromonomers,oligomers or reactive compounds).

The silicone product 100 comprises polymer molecules 110 of the group ofpolysiloxanes. Often the term silicone is used instead of a material ofthe group of polysiloxanes. Polysiloxanes are a polymeric material withthe general formula [R1R1SiO]m wherein R1 and R2 are an organic group,such as, for example, methyl, ethyl or phenyl. R1 may be equal to R2.The backbone of the molecules is an inorganic Silicon-Oxygen chain . . .—Si—O—Si—O—Si—O— . . . In FIG. 1 the polymer molecules 110 are drawn asirregular lines which represent the Silicon-Oxygen chain. The materialformed by the polymer molecules 110 is light transmitting, which meansthat light can be transmitted through the material—in other words, notmuch light is absorbed by the material, for example, not more than 15%of the light is absorbed. In another embodiment, light transmittingmeans not more than 10% of the light is absorbed. It is to be noted thatthe material may be clear (transparent) or may be diffuse lighttransmitting (translucent).

The silicone product 100 further comprises filler particles 120. Thefiller particles are light transmitting. Thus, when only fillerparticles 120 would be provided in the material of polysiloxanemolecules 110, the combination of them would still be lighttransmitting. It is to be noted that the filler particles may influenceoptical characteristics of the material. For example, if a differencebetween the refractive index of the filler particles and the refractiveindex of the material of polysiloxane molecules 110 is relatively largeand if the size of the filler particles is comparable to the wavelengthof (visible) light or larger, the filler particles partially reflectlight which impinges on them and partially transmit and refractlight—this results in a more diffuse/translucent silicone product 100.

The filler particles 120 are of an inert material. In the context ofthis document inert materials are materials which do not react with atleast the materials which are used in the context of this document underthe circumstances described in the context of this document. Thus, theinert materials are not chemically reactive. This does not exclude thatunder specific circumstances the inert materials may be involved in achemical reaction, but in such situations, large amounts of energy fromheat, pressure or radiation are needed and often catalysts are used toassist reactions which the inert materials. Thus, the material of thefiller particles 120 does not react with the polysiloxane molecules 110,with materials added to the polysiloxane molecule 110 to create a resin,etc. under normal atmospheric conditions, during use in a lightingassembly, and/or in combination with later discussed materials (such asluminescent materials). As will be discussed later, the filler particles120 may have a layer of an organic material at their surface. In certaincircumstances, this layer may be reactive with the polymer molecule 110when the silicone product 110 is cured.

An advantageous material for the filler particles is silica. Silica(SiO2) is often used within a material which comprises a polysiloxaneand in many optical applications the amount of silica used in a siliconemay peak at 30 or even at 40 weight percent (wt %) of the total weightof the silicone resin. Other suitable materials from which transparentinert particles can be manufactured are materials from the groups ofalumina, titania, silica or, for example, a clay. Specific types oftransparent clays can be used and, in general, these particles have arelatively flat shape and thus a relatively large outer surface alongwhich the luminescent particles 130 may be distributed. Flat shapedparticles provide an advantageous spatially separation of theluminescent particles 130.

The silicone product 100 further comprises luminescent material whichcomprises luminescent particles 130 of a material which shows quantumconfinement and has at least in one dimension a size in the nanometerrange. Quantum confinement means that the particles have opticalproperties that depend on the size of the particles. The luminescentparticles 130 are configured to absorb a portion of light which impingeson them and to convert a portion of the absorbed light into light ofanother color. The luminescent particles 130 of the luminescent materialhave in at least one dimension a size which is in the nanometer range.This means, for example, that, if the particles 130 are substantiallyspherical, their diameter is in the nanometer range. Or, this means, forexample, if they are rod-shaped, that a size of a cross-section of therod is in one direction in the nanometer range. A size in the nanometerrange means that their size is at least smaller than 100 nanometers,thus, smaller than 0.1 micrometer, and larger or equal to 0.5nanometers. In an embodiment, the size in one dimension is smaller than50 nanometers. In another embodiment, the size in one dimension is inthe range from 2 to 20 nanometers. Examples of suitable luminescentparticles 130 are quantum dots, quantum rods and quantum tetrapods. Inanother embodiment, the luminescent particles 130 do not show quantumconfinement. For example, Mn-doped ZnSe quantum dots show a lightemission of the Mn-ions and, thus, is the light emission of thesequantum dots independent of the size of the quantum dots.

Quantum dots are small crystals of semiconducting material generallyhave a width or diameter of only a few nanometers. When excited byincident light, a quantum dot emits light of a color determined by thesize and material of the crystal. Light of a particular color cantherefore be produced by adapting the size of the dots. Most knownquantum dots with emission in the visible range are based on cadmiumselenide (CdSe) with shell such as cadmium sulfide (CdS) and zincsulfide (ZnS). Cadmium free quantum dots such as indium phosphode (InP),and copper indium sulfide (CuInS2) and/or silver indium sulfide (AgInS2)can also be used. Quantum dots show very narrow emission band (forexample, with a width of 50 nanometer, or even 25 nanometer, expressedas a Full Width Half Maximum (FWHM) value) and, thus, they showsaturated colors. Furthermore the color of the light can easily be tunedby adapting the size of the quantum dots. Any type of quantum dot knownin the art may be used in the present invention. Other examples ofmaterials of which quantum dots are made are: ZnSe, Silicon, CuInS,Carbon, ZnO, and Mn-doped materials. Other types of nanosizedluminescent materials are silver clusters, or other magic-sized noblemetal clusters.

Quantum rods typically consist of a CdSe quantum dot core, surrounded bya rod-shaped CdS shell, which can have aspect ratios of 2 to 20. Thiscould also be an InP quantum dot core, surrounded by a rod-shaped shellof similar dimensions. In another case the rod comprises CdSe or InProd-shaped nanocrystal, surrounded by a few monolayers of inorganicshell materials like CdS or ZnS. A tetrapod comprises a core of, forexample, CdSe or InP, surrounded by a shell of material that preferablygrows on certain facets of the nanocrystal such that a nanocrystal witha tetrapod-shape results. Finally, the recently reported nanoplatelets(Ithurria et al, Nature Materials 2011) are also included as luminescentnanomaterials. These materials are platelets of only a few (2-20)monolayers of eg CdSe or InP, and have much larger dimensions in theother two direction. Quantum confinement hence takes place in only onedirection.

The luminescent particles 130 and the filler particles 120 are wellmiscible with each other. This means that they do not show the tendencyto go away from each other when they are, for example dissolved in amedium/liquid in which they are able to move freely. In a subsequentstep, the luminescent particles are brought to flocculate. In thisprocess they heteroflocculate onto the surface of the filler particlesand they will stay there. Thus, when the luminescent particles 130 arebrought in contact with filler particles 120, they remain in contactwith the filler particles. When the luminescent particles 130 are in anon-compatible fluid or resin, they show the tendency to agglomerate,aggregate and/or flocculate, however, when they are on the surface of afiller material, they remain mainly at their position. Often the term“chemical affinity” is used to describe the well-miscibility of twomaterials. In practical embodiments, it means that the filler particles120 and the luminescent particles 130 can both be homogeneously mixedinto at least one type of solvent. In other practical embodiment, theparticles 120, 130 are both compatible with more than one solvent.

In the silicone product 100 the luminescent particles 130 aredistributed along the outer surfaces of the filler particles 120. Thismeans that the luminescent particles 130 touch a filler particle 120.Both materials remain in contact with each other in the silicone product100. Due to this the luminescent particles remain homogenouslydistributed in the silicone product. In general, luminescent particles130, which show quantum confinement and have one dimension in thenanometer range, are not well miscible with a material which comprisespolysiloxane molecules 110. Especially this results in the fact that theluminescent particles 130 remain in the silicone product 100 in contactwith the filler particles 120. When the luminescent particles 130 are incontact with filler particles 120 they do not have any more the tendencyto flocculate or agglomerate and thus remain spatially separated. Whenthe luminescent particles 130 are well spatially separated, they providean advantageous color conversion efficiency—hence, their quantumefficiency is relatively high. It is to be noted that in anotherembodiment, the filler particles may be porous and that the luminescentparticles are not only present at the ‘outer’ surface of the fillerparticles, but also at the ‘inner’ surfaces of the filler particles.

In an embodiment, at least 60% of the luminescent particles 130 areseparated far enough from other luminescent particles 130 to prevent areduction of quantum efficiency of these particles. In an embodiment atleast 75% of the luminescent particles 130 are separated far enough fromother luminescent particles 130. In yet another embodiment, at least 90%of the luminescent particles 130 are separated far enough from otherluminescent particles 130 Separated far enough from each other meansthat these particles at least do not touch each other and they arespaces apart at a distance which prevents concentration quenching. Theeffect of these embodiment is that the quantum efficiency, and thus thecolor conversion efficiency, of the silicone product 100 as a whole isrelatively high. In an embodiment, the luminescent particles 130 thatare separated far enough from other luminescent particles 130 have atleast a distance of 7 nanometers between the each other without anotherluminescent particles 130 in between them. However, in some situations,as shown in FIG. 1 at location 132, still some luminescent particles maybe in contact with each other or within a distance of 7 nanometers fromeach other.

As drawn in FIG. 1, in an embodiment, the filler particles 120 arelarger than the luminescent particles 130. However, the size of thefiller particles 120 may be equal to the size of the luminescentparticles 130. If the filler particles 120 are larger than theluminescent particles 130 the luminescent particles 130 will be betterspatially separated by the filler particles.

The relative amount of filler particles 120 within the silicone productis below 40 wt %, and in another embodiment, below 30 wt %. The relativeamount of luminescent particles 130 mainly depends on the lightconversion requirements. In an embodiment, their relative amount isbetween 0.1 wt % and 10 wt %. In another practical embodiment, theirrelative amount is between 0.5 wt % and 5 wt %. To obtain anadvantageous spatially separation of the luminescent particles 130 inthe silicone product 100, the relative amount of filler particles 120 islarger than the relative amount of luminescent particles 130 (when beingexpressed in a weight percentage). An even better spatially separationof the luminescent particles 130 is obtained in the silicone product 100if the relative amount of filler particles 120 is 10 wt % larger thanthe relative amount of luminescent particles 130.

It is to be noted that in FIG. 1 the cross-sectional shapes of thefiller particles 120 and the luminescent particles 130 is circular orelliptical. The drawn shapes are purely schematic and the fillerparticles 120 and the luminescent particles 130 may have completelydifferent shapes.

Optionally not more than 20%, or not more than 10% of the surface of thefiller particles 230 is covered by particles 130 of the luminescentmaterial. To determine the relative amount of the surface of the fillerparticles 230 being covered by the particles 130 of the luminescentmaterial, it is reasonable to assume that the filler particles arespherical and non-porous. Further, based on TEM imaging, one maydetermine for a sample of the silicone product an average size of thefiller particles, an average size of the particles of luminescentmaterial and an average number of particles of luminescent materialbeing in contact with the filler particles. Based on these numbers onemay determine how large the average surface of an average sphericalfiller particle is. Further, the area covered by a single particle ofthe luminescent material is a projection of the surface area of thesingle particle of the luminescent material on the surface of the fillerparticle. For example: if the average diameter of a silica fillerparticles is, for example, 100 nm, the average surface area of suchparticles is 1.10-14 m2. If the average diameter of the of quantum dotsparticles is, for example, 7 nm, the area of the surface of the silicafiller particles is 4.10-17 m2. When the average amount of quantum dotson a single silica filler particle is 10, the average area coverage is0.04=4%.

FIG. 2 schematically shows an embodiment of a filler particle 220 withtwo particles 230 of a luminescent material being in contact with asurface of the filler particle 220. The silicone product 100 of FIG. 1may comprise a multitude of such filler particles 220 and luminescentparticles 230. The drawing of FIG. 2 presents a cross-sectional view ofthe filler particle 220 and the luminescent particles 230. The fillerparticle 220 has in a cross-sectional view a shape similar to a hexagon,and in other embodiments, the cross-sectional shape may be different.The surface of the filler particle 220 comprises a first layer 222 of anorganic material. The first layer 222 may be a monolayer, which meansthat it is a layer which is only one molecule thick. The luminescentparticles 230 are in contact with the filler particle 220, which meansthat the luminescent particles 230 are distributed along the surface ofthe filler particle 220. The surface of the luminescent particles 230comprises a second organic layer 232. In an embodiment, the secondorganic layer 232 is a monolayer.

In FIG. 2 light 242 is schematically drawn by means of an arrow. Light242 impinges on one of the luminescent particles 230 and is at leastpartially absorbed by the respective luminescent particles 230. Therespective luminescent particle converts the absorbed light towardslight 244 of another wavelength. The another luminescent particle 230receives light 246 and the another luminescent particle 230 may bearranged to convert the absorbed light to yet another wavelength 248. Itis noted that in the context of the invention different luminescentparticles 230 may be used. They may be differently with respect to thecolor of light which is being emitted and this color strongly depends onthe size of the particle 230. All luminescent particles 230 show quantumconfinement and have a size in a specific dimension which is in thenanometer range.

In FIG. 2 a size of the luminescent particle 230 is indicated by d2. Ina cross-sectional view, a width of the luminescent particle 230 is inthe nanometer range, which means that the width is in the range from 1to 100 nanometers. The cross-sectional view of FIG. 2 may be across-section of a spherical luminescent particle, or the cross-sectionof, for example, a wire shaped particle. Other cross-sectional shapesare also possible. In FIG. 2 also a maximum size of the filler particle220 is indicated by d1max. Maximum size means that no other line whichintersects the filler particle 220 intersects the particle along alonger length than the maximum size. In an embodiment, the size of thefiller particles is below 5 micrometer, or, in another embodiment, below1 micrometer, or, in a further embodiment, below 500 nanometers. In yetanother optional embodiment below 250 nanometers, and in a furtheroptional embodiment smaller than 100 nanometers. When the fillerparticles have a smaller size, the total area of the filler particlessurface is larger and, thus, the particles of luminescent material aredistributed along a relatively larger surface which increases theprobability that the particles of luminescent material are betterspatially separated. The smaller the filler particles are, the largertheir surface area expressed as m2/gram. However, it is advantageous ifthe filler particles are at least two or three times larger than theparticles of luminescent material to obtain a good spatial separation ofparticles of luminescent material which are in contact with a singlefiller particle.

FIG. 3 schematically shows a lighting unit 500 according to the secondaspect of the invention. The lighting unit comprises a housing 302 whichhas a light exit window at which a light transmitting layer 301 isarranged. In an example, the light transmitting layer may be a diffuser.In yet another example, the light transmitting layer is a layer ofmicro-collimators. Inside the housing is arranged a solid state lightemitter 306 which is configured to emit light of a first spectrumtowards the light exit window of the housing. The interior of thehousing 302 is filled with the silicone product 304 according to thefirst aspect of the invention. The silicone product 304 is providedwithin the housing to provide a better outcoupling of light from thesolid state light emitter 306 and to provide an advantageous lightguiding of the outcoupled light towards the light exit window. Theluminescent particles of the silicone product 304 receive the light ofthe first spectrum and absorb at least a portion of this light. Theluminescent particles convert a portion of the absorbed light towardslight of a second spectrum. Depending on the amount of luminescentparticles in the silicone product 304, the first spectrum and the secondspectrum will be emitted into the ambient in a specific ratio whichdetermines the color of the light emitted by the lighting unit 300. Thelighting unit 300 is relatively efficient. The luminescent material inthe silicone product 304 provide a high quantum efficiency, and thesilicone product 304 assist in the outcoupling of light from the solidstate light emitter 306, and, thus, not much light is trapped in thesolid state light emitter 306. Examples of solid state light emittersare Light Emitting Diodes (LEDs), Organic Light Emitting diode(s) OLEDs,or, for example, laser diodes. It is to be noted that the invention isnot limited to lighting units 300 of which the interior space is fullyfilled with the silicone product 304. In specific embodiments, theinterior space is partially filled with silicone and partially filledwith the silicone product according to the first aspect of theinvention.

FIG. 4 schematically presents an embodiment of a method 400 ofmanufacturing a silicone product comprising immobilized luminescentmaterial. In step 402 a mixture of filler particles of a lighttransmitting inert material and a luminescent material is obtained. Theluminescent material comprises particles showing quantum confinement andhave at least in one dimension a size in the nanometer range. In themixture, the particles of the luminescent material are situated at asurface of the filler particles. In a subsequent step 404 the mixtureobtained in step 402 is mixed with a polymeric material which comprisesa material of the group of polysiloxanes. The luminescent material mayalso comprise material which has, in at least one dimension, a size inthe nanometer range, but does not show quantum confinement.

The particles of luminescent material are at the surface of the fillerparticles and are thus immobilized. This means that, when the mixture ismixed with the polymeric material, the particles of luminescent materialdo not flocculate or aggregate and remain at the surface of the fillerparticles and, thus, is the quantum efficiency of the luminescentmaterial not negatively influenced when being applied in the polymericmaterial.

The step 402 of obtaining the mixture of filler particles and theluminescent material may, optionally, be subdivided in the subsequentsteps:

-   -   obtaining 406 a first homogeneous mixture of filler particles in        a first solvent,    -   obtaining 408 a second homogeneous mixture of filler particles        in a second solved,    -   mixing 410 the first homogeneous mixtures with the second        homogeneous mixture to obtain a third homogeneous mixture,    -   flocculating 412, 414 the luminescent material on the filler        particles by changing 412 a solvent composition of the third        homogeneous mixture or changing 414 a solvent quality of the        third homogeneous mixture.

In the above discussed steps, the filler particles may be hydrophobizedsilica particles and the first solvent is often a suitable nonpolar orslightly polar solvent. Examples of suitable material for the firstsolvent are: toluene, xylene, butyl acetate or hexamethyldisiloxane, orlonger alcohols like n-decanol. If the particles of the luminescentmaterial are quantum dots, they are typically diluted from a stocksolution into the second solvent to form a stable dispersion. The secondsolvent may be the same solvent as the first solvent or at least onesolvent of a similar type.

Changing 412 the solvent composition of the third homogeneous mixturemay be performed by adding a third solvent to the third homogeneousmixture. Solvents which are more polar than the first solvent and secondsolvent are effective to establish the flocculation. Also some specificother nonpolar can cause the flocculation of the luminescent material onthe filler particles. An example of a more polar solvent is propylenecarbonate. The boiling point of propylene carbonate is relatively high(240° C.), which is advantageous when the solvents are removed from themixture by thermal treatment; the first solvent and second solvent willbe removed before the third solvent is removed, and, thus, thelikelihood that the particles of luminescent material stay on thesurface of the filler particles is increased. Optionally, in the step ofmixing 404 the obtained mixture of step 402 with a polymeric materialcomprising a material of the group of polysiloxanes, the third solventmay still be present in the obtained mixture. Often, the polymericmaterial also comprises a fourth solvent and when the mixture of thepolymeric material and the mixtures of luminescent particles at fillerparticles surfaces is cured, in an advantageous embodiment, the fourthsolvent is removed before the third solvent is removed.

Alternatively, the solvent quality of the third homogeneous mixtures maybe changed 414 by changing the temperature of the third homogeneousmixture. With suitable solvents, heating or cooling result in theflocculation of quantum dots and thus in flocculating the luminescentmaterial on the filler particles. For example, the luminescent particlesare colloidally stable in the subsequent solvents at room temperature,but flocculate at −18° C.: dipropylene glycol dimethylether, iso butylacetate, methyl isobutyl keton and n-amyl acetate.

Additionally and optionally, the third homogeneous mixture is dried 416.Drying may, for example, be performed by heat treatment and/or bycreating a vacuum.

The step of mixing 404 the mixture of filler particles and theluminescent material with the polymeric material may be followed by astep of curing 420 the mixture obtained in step 404.

It is to be noted that, unless otherwise explained, the order of thesteps of the method may be different or some steps may be executed inparallel. For example, the steps 406 and 408 of obtaining the firsthomogeneous mixture and obtaining the second homogeneous mixture may beexecuted in parallel or in another order.

In a comparative test two samples were manufactured. A first sample wasmanufactured according to the state of the art methods of manufacturinga silicone product containing luminescent material, and a second samplewas manufactured according to the invention.

The first sample was manufactured as follows: 15 μl of a stock solutionof quantum dots (10% w/v) was diluted in 1 ml toluene. The dilutedsolution was added to a 70% silicone (KJR9226) in toluene solution.Layers of the silicone product were prepared by drop-casting. Especiallyfor creating a Transmission Electron Microscopy (TEM) image, a thinlayer was prepared by quickly removing excess liquid on the TEM windowusing capillary forces. The layers were cured, 5 minutes at 50° C., 5minutes at 100° C. and 30 minutes 15 150° C. It was observed in the TEMimage that the quantum dots formed clusters, for example, with adiameter of around 100 nm. Two dimensional and three dimensionalclusters were found in the sample. A limited amount of quantum dots werefound as single quantum dots.

The second sample was manufactured as follows: 0.1 g of silica (WP-300)was dispersed in 1 ml of 1-decanol (bp=233° C.). 15 μl of a stocksolution of quantum dots (10% w/v) was diluted in 1 ml of 1-decanol.These two dispersions were added together. An amount of 0.2 ml propylenecarbonate was added which was enough to cause flocculation of thequantum dots. Thereafter the sample was left stirring for 15 minutes.Subsequently, 0.6 ml of silicone resin (KJR9226—50% in phenetole(bp=170° C.)) was added. Layers of the silicone product were prepared bydrop-casting. Especially for creating a Transmission Electron Microscopy(TEM) image, a thin layer was prepared by quickly removing excess liquidon the TEM window using capillary forces. The layers were cured, 5minutes at 50° C., 5 minutes at 100° C. and 30 minutes 15 150° C. It wasobserved in the TEM image that hardly any free quantum dots were presentand that the quantum dots are attached to the silica particles. Most ofthe quantum dots were spaced at some distance from other quantumdots—only a minor number of quantum dots formed small clusters ofquantum dots at the surface of the silica particles.

It should be noted that the above-mentioned embodiments illustraterather than limit the invention, and that those skilled in the art willbe able to design many alternative embodiments without departing fromthe scope of the appended claims.

In the claims, any reference signs placed between parentheses shall notbe construed as limiting the claim. Use of the verb “comprise” and itsconjugations does not exclude the presence of elements or steps otherthan those stated in a claim. The article “a” or “an” preceding anelement does not exclude the presence of a plurality of such elements.The invention may be implemented by means of hardware comprising severaldistinct elements. In the product claim enumerating several means,several of these means may be embodied by one and the same feature. Themere fact that certain measures are recited in mutually differentdependent claims does not indicate that a combination of these measurescannot be used to advantage.

1. A method of manufacturing a silicone product comprising immobilizedluminescent material, the method comprises the steps of: obtaining amixture of filler particles of a light transmitting inert material and aluminescent material comprising luminescent particles showing quantumconfinement and having at least in one dimension a size in the nanometerrange, wherein the luminescent particles are situated at a surface ofthe filler particles, mixing the mixture with a polymeric materialcomprising a material of the group of polysiloxanes.
 2. The method ofmanufacturing a silicone product according to claim 1, wherein the stepof obtaining a mixture comprises the steps of: obtaining a firsthomogeneous mixture of the filler particles in a first solvent,obtaining a second homogeneous mixture of the luminescent material in asecond solvent, mixing the first homogeneous mixture with the secondhomogeneous mixture to obtain a third homogenous mixture, andflocculating the luminescent particles on the filler particles bychanging a solvent composition or a solvent quality of the thirdhomogeneous mixture.
 3. The method of manufacturing a silicone productaccording to claim 1, wherein the luminescent particles distrusted onthe surface of the filler particles are immobilized in the polymericmaterial.
 4. The method of manufacturing a silicone product according toclaim 1, further comprising curing the polymeric material.